Pyridyloxy-phenoxyalkanecarbonyl oxime derivatives

ABSTRACT

Herbicidal and plant growth-regulating pyridyloxy-phenoxyalkanecarboxylic acid derivatives of the formula ##STR1## wherein A is cyano or carboxyl, an ester, thioester or amido radical or the salt of the carboxylic acid with a cation or a quaternary ammonium group, 
     Z is hydrogen, halogen, cyano, nitro, C 1  -C 4  alkyl or C 1  -C 4  alkoxy, 
     D is hydrogen, halogen, cyano, nitro or C 1  -C 4  alkoxy, 
     E is halogen, trifluoromethyl or cyano. 
     R 1  is hydrogen, C 1  -C 4  alkyl, C 2  -C 8  alkoxyalkyl or C 1  -C 5  alkoxy carbonyl and 
     R 2  is hydrogen or C 1  -C 4  alkyl.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 140,402 filed on Apr. 14,1980, now U.S. Pat. No. 4,329,167, which is a continuation-in-part ofapplication Ser. No. 080,965 filed on Oct. 1, 1979, now abandoned.Application Ser. No. 080,965 was a continuation of application Ser. No.919,119, filed on June 26, 1978, now abandoned.

DETAILED DISCLOSURE

The present invention relates to novelpyridyloxy-phenoxyalkanecarboxylic acid derivatives which have aherbicidal and plant growth-regulating action, processes for theirproduction, compositions which contain these compounds as activeingredients, and to a method of selectively controlling weeds and ofregulating plant growth which comprises the use of the novel activesubstances or of compositions which contain them.

The active compounds of the present invention have the formula I##STR2## wherein

A represents the cyano group, a radical --COB or a 2-oxazoline radicalwhich is unsubstituted or mono- or polysubstituted by methyl,

B represents a radical --OR₃, --SR₃, --NR₄ R₅ or --O--N═C (C₁ -C₄alkyl)₂ Z and D each individually represent hydrogen, halogen, cyano,nitro, C₁ -C₄ alkyl or C₁ -C₄ alkoxy,

E represents halogen, trifluoromethyl, cyano or nitro,

R₁ represents hydrogen, C₁ -C₄ alkyl or C₂ -C₈ alkoxyalkyl, or C₁ -C₅alkoxycarbonyl

R₂ represents hydrogen or C₁ -C₄ alkyl,

R₃ represents hydrogen, ammonium or an alkali or alkaline earth metalcation, a benzyl or C₁ -C₄ alkylammonio group, whose alkyl radicals maybe substituted by hydroxyl C₁ -C₄ alkoxy or

a C₁ -C₁₈ alkyl radical which is unsubstituted or substituted byhalogen, cyano, C₁ -C₈ alkoxy, C₂ -C₈ alkoxyalkoxy, C₂ -C₈alkoxycarbonyl, bis(C₁ -C₄ alkyl)amino, C₃ -C₈ cycloalkyl, C₃ -C₈cycloalkenyl and also by a 5 to 6-membered heterocyclic radical which isunsubstituted or is itself mono- or polysubstituted by C₁ -C₄ alkyl;

a C₃ -C₁₀ alkenyl radical which is unsubstituted or mono- totetrasubstituted by halogen;

a C₃ -C₈ alkynyl, C₃ -C₈ cycloalkyl- or C₃ -C₈ cycloalkenyl radical;

a phenyl or benzyl radical, which is mono- or polysubstituted byhalogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, nitro,trifluoromethyl, cyano, carboxyl, sulfonyl, hydroxyl, amino or bis(C₁-C₄ alkyl)amino;

a 5 to 6-membered heterocyclic radical;

R₄ represents hydrogen, a C₁ -C₈ alkyl radical, unsubstituted orsubstituted by halogen, hydroxyl, cyano, C₁ -C₄ alkoxy or C₁ -C₄alkoxycarbonyl;

C₃ -C₈ alkenyl, unsubstituted or halogensubstituted;

C₃ -C₈ alkynyl, C₃ -C₈ cycloalkyl or C₃ -C₈ cycloalkenyl;

phenyl or benzyl, unsubstituted or substituted by halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy, trifluoromethyl, nitro or cyano;

R₅ represents the same as R₄ or C₁ -C₄ alkoxy or C₂ -C₄ alkenyloxy or R₄and R₅ together with the nitrogen atom, to which they are attached, formalso a 5 to 6-membered heterocyclic ring, which may be substituted by C₁-C₄ alkyl.

In the above formula the alkyl radicals can be branched or unbranchedand contain the indicated number of carbon atoms. The heterocyclicradicals R₃ include, furyl-, tetrahydrofuryl-, oxane-,thiophene-radicals and further, the same that are also found by thesymbols R₄ and R₅ with the nitrogen to which they are attached,pyrrolidine, pyridine, piperidine, morpholine, oxazoline or piperazine.These rings may be substituted by C₁ -C₄ alkyl radicals.

The active compounds of the formula (I) of the present invention possessa herbicidal action, especially in post-emergent application, and can beused as weed-killers in crops of mono- and dicotyledonous plants. Theyalso possess advantageous growth-regulating effects (growth inhibition).In particular, they inhibit the growth of dicotylendonous plants.Exemplary of the useful application of the compounds of the presentinvention are:

the reduction of the vegetative growth in soya and similar leguminosae,resulting in an increase in the yield of these plants;

the inhibition of the undesirable growth of suckers in tobacco plants,the leading shoots of which have been cut, thus promoting the formationof larger and finer leaves;

the inhibition of the growth of grass and dicotyledonous plants, such asfruit trees, ornamental trees, bushes and hedgerows, with the object ofsaving cutting work.

The compounds of the present invention have a low toxicity towarm-blooded animals and their application causes no problems. The rateof application is between 0.1 and 5 kg per hectare.

Good herbicidal activity has been observed with the groups of compoundslisted below. They are therefore of special interest among the compoundsof formula I. ##STR3##

In these formulae, B has the meanings given above under formula I.

From the U.S. Pat. No. 4,046,533 and 4,105,435 have become know4-pyridyloxy-phenoxyalkanecarboxylic acid derivatives with herbicidalactivity. The compounds of this invention proved to act differently andare capable of controlling plants, which were not or not satisfactorilycontrolled with compounds known from these patents.

The novel compounds of the formula (I) can be obtained by processeswhich are in themselves known. In a first process, a substituted orunsubstituted halopyridine of the formula II, ##STR4## wherein D and Eare as defined in formula (I) and Hal represents a halogen atom,preferably a chlorine or bromine atom, is reacted with ahydroxyphenoxyalkanecarboxylic acid derivative of the formula III,##STR5## wherein A, Z, R₁ and R₂ are as defined in formula (I), in thepresence of an acid acceptor.

Such reactions are in themselves known and the exact method by whichthey are carried out is described in the literature, for example inHouben-Weyl, Volume 3, page 85 ff.

In a second process, the pyridyloxy-phenoxyalkanecarboxylic acidderivatives of the formula (I) are prepared by reacting apyridyloxy-hydroxyphenyl ether of the formula IV, ##STR6## wherein Z, Dand E are as defined in formula (I), with an α-halogenocarboxylic acidderivative of the formula V ##STR7## wherein A, R₁ and R₂ are as definedin formula (I) and Hal represents a halogen atom, preferably a chlorineor bromine atom, in the presence of an acid acceptor.

The above reactions can be carried out in the presence or absence ofsolvents or diluents which are intert to the reactants. Polar organicsolvents, such as methyl ethyl ketone, acetonitrile, dimethyl formamide,dimethyl sulphoxide etc., are preferred. The reaction temperatures arebetween 0° and 200° C. and the reaction time is from 1/4 hour to severaldays, depending on the chosen reaction temperature and solvent. Thereaction is ordinarily carried out under normal pressure or slightexcess pressure. Suitable acid acceptors for the reaction are inorganicbases, for example NaOH, KOH, NaOCH₃, NaH, K₂ CO₃, potassiumtert-butylate etc., and also organic bases.

A number of the starting materials of the formulae (II) to (V) areknown. Starting materials of these formulae which have not yet beendescribed can be easily prepared by conventional processes andtechniques.

Substituted 2-halogeno-pyridines of the formula (II) can be easilyobtained from the corresponding 2-pyridinoles, some of which are known.Starting materials of the formula (III) can be obtained by reacting, forexample, a monobenzyl ether of an optionally substituted resorcinol withan α-halogenocarboxylic acid derivative, preferably an ester of theformula (V), and cleaving the benzyl-phenyl ether bond by catalytichydrogenation, for example with a palladium on carbon catalyst, wherebythe benzyl radical is removed as toluene.

The starting materials of the formula (IV) can be obtained by reactionof resorcinol with halopyridines in equimolar amounts and in thepresence of a base.

Carboxylic acid derivatives of the formula (V) are also known. As theirsimplest respresentatives, mention may be made for example ofchloroacetic acid and the esters, thioesters and amides thereof.However, other α-halocarboxylic acid derivatives substituted inaccordance with R₁ and R₂ are also suitable.

The following Examples illustrate the process of the present inventionfor obtaining arbitrarily chosen active compounds of the formula (I).Further active compounds which are obtained in corresponding manner arelisted in the subsequent tables.

These pyridyloxy-phenoxyalkanecarboxylic acid derivatives of the formula(I) are stable compounds which are soluble in conventional organicsolvents, such as alcohols, ethers, ketones, dimethyl formamide,dimethyl sulphoxide etc.

EXAMPLE 1 α-[3-(3',5'-Dichloropyrid-2-yl)-oxy-phenoxy]propionic acidmethyl ester (intermediate) ##STR8##

30.8 g (0.1 mole) of 3-(3',5'-dichloropyrid-2'-yl)-oxy-phenoxy phenol,18.2 g (0.13 mole) of potassium carbonate and 22 g of methylα-bromopropionate are refluxed in 300 ml of ethyl ketone for 3 hours.The inorganic salts are then filtered off and the filtrate isconcentrated. Recrystallisation of the residue from ether/petroleumether affords 29 g (70% of theory) of the title product with a meltingpoint of 58°-60° C.

EXAMPLE 2 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy]propionicacid methyl ester ##STR9##

(a) 171 g (0.5 mole) ofα-[3-(3',5'-dichloropyrid-2-yl)oxy-phenoxy]propionic acid (preparedaccording to Example 1) are dissolved in 250 ml of 1,2 dichloroethane.The reaction is then cooled to -12° to -14° C. and during 2 hours thereis added dropwise 250 ml of 100% nitric acid. After 1/2 hour, thereaction mixture is poured into ice-water. The mixture is then extractedmethylene chloride. The organic phase is washed twice with water, driedover magnesium sulfate and evaporated. The residue is taken up in 500 mlof hexane and triturated, which causes it to crystallise. The cristalsare filtered and dried to yield 172.3 g (89% of theory) of the titlecompound which melts at 107°-108° C.

This compound can also be produced in the following manner.

(b) 30.1 g (0.1 mole) of 3-(3',5'-dichloropyridyl-2'-oxy)-6-nitrophenol,16.7 g (0.1 mole) of methyl α-bromopropionate and 20.7 g (0.15 mole) ofpotassium carbonate are refluxed for 14 hours in 400 ml of methyl ethylketone. The inorganic salts are filtered off and the filtrate isconcentrated. The residual brown oil is taken up in chloroform andfiltered over a short column of silica gel, affording 22.4 g (58% oftheory) of title product which melts at 107° C. after recrystallisationfrom hexane.

EXAMPLE 3 3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenyl acetate(intermediate)

A mixture of 256 g of 3-(3',5'-dichloropyridyl-2'-oxy)-phenol, 1.9liters of glacial acetic acid and 280 ml of acetic anhydride is stirredfor 12 hours at reflux temperature. The solution is cooled to 40° C.,then 81 g of sodium acetate are added with stirring and 106 g ofchlorine gas are introduced at 40° C. in the course of 7 hours. Excesschlorine gas is removed by introducing nitrogen for 2 hours and thesolution is concentrated. The ethyl acetate solution (1000 ml) of theoily residue is washed with water and saturated NaHCO₃ solution andconcentrated, affording 343 g of the title compound as a brown oil whichcrystallises spontaneously on trituration with petroleum ether. Meltingpoint: 71°-75° C.

EXAMPLE 4 3-(3',5'-Dichloropyridyl-2'-oxy)-6- and 4-chlorophenol(intermediate)

A suspension of 2.26 g of powdered KOH and 10 g of3-(3',5'-dichloropyridyl-2'-oxy)-6-phenyl acetate in 30 ml of absolutemethanol is stirred for 20 minutes at 60° C. in a nitrogen atmosphere,cooled to room temperature, acidified with 3.7 ml of concentratedhydrochloric acid and concentrated. The toluene solution (50 ml) of theresidue is washed with water, dried, filtered over activated carbon andconcentrated, affording 8.4 g of an oil which consists of a mixture ofthe 6-chlorophenol and 4-chlorophenol isomers in the ratio 7:3.

EXAMPLE 5 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenoxy]propionicacid methyl ester ##STR10##

25 g (0.085 mole) of a mixture of3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenol and3-(3',5'-dichloropyridyl-2'-oxy)-4-chlorophenol (prepared according toExample 4), 14.2 g (0.085 mole) of methyl α-bromopropionate and 13.8 g(0.1 mole) of potassium carbonate are refluxed for 6 hours in 250 ml ofmethyl ether ketone. The inorganic salts are filtered off and thefiltrate is concentrated. The residual yellow oil is recrystallised fromether/petroleum ether, affording 30.1 g (94% of theory) if isomer-freetitle product with a melting point of 82°-83° C.

EXAMPLE 6 3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenyl acetate(intermediate)

A mixture of 205 g of 3-(3',5'-dichloropyridyl-2'-oxy)-phenol, 1.1liters of glacial acetic acid and 224 ml of acetic anhydride is stirredfor 12 hours at reflux temperature. The solution is cooled to 60° C.,then 64.8 g of sodium acetate are added with stirring and a solution of102 ml of bromine in 400 ml of glacial acetic acid are added dropwise at60° C. in the course of 53/4 hours. The solution is concentrated and theresidue is dissolved in ethyl acetate. The organic phase is washed insuccession with water and saturated NaHCO₃ solution. The combined ethylacetate extracts are dried and concentrated, affording 302.5 g of an oilwhich crystallises on being covered with a layer of petroleum ether(b.p. 60°-90° C.). After recrystallisation from cyclohexane, the titleproduct melts at 106°-107° C.

EXAMPLE 7 3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenol (intermediate)

A suspension of 28 g of powdered KOH and 153.5 g of3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenyl acetate in one liter ofabsolute methanol is stirred for 20 minutes at 60° C. in a nitrogenatmosphere and concentrated. The concentrate is acidified at roomtemperature with concentrated hydrochloric acid and evaporated todryness. The toluene solution (400 ml) of the residue is washed withwater, dried, and concentrated. The oily residue is triturated withpetroleum ether/cyclohexane and filtered, according 137 g of thecrystalline title product with a melting point of 93°-95° C.

EXAMPLE 8 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenoxy]propionicacid methyl ester ##STR11##

50.2 g (0.15 mole) of 3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenol(prepared according to Example 7), 27.5 g (0.165 mole) of methylα-bromopropionated and 27.6 g (0.2 mole) of potassium carbonate arerefluxed for 5 hours in 250 ml of methyl ether ketone. The inorganicsalts are filtered off and the filtrate is concentrated. The residualreddish oil is recrystallised from ether/petroleum ether, affording 58 g(91.8% of theory) of the title compound with a melting point of 75° C.

Analogously to these Examples, the following compound can be prepared:

    ______________________________________                                         ##STR12##                                                                      No.       B                   phys. data                                    ______________________________________                                        1 OCH.sub.3 m.p. 82-83°                                                2 OC.sub.2 H.sub.5                                                                        m.p. 53-56°                                                3 OC.sub.3 H.sub.7 iso                                                                    n.sub.D.sup.25 1.5567                                             4 OC.sub.3 H.sub.7 n                                                          5 OC.sub.4 H.sub.9 n                                                                      n.sub.D.sup.25 1.5540                                             6 OC.sub.4 H.sub.9 sec.                                                                   n.sub.D.sup.25 1.5525                                             7 OC.sub.4 H.sub.9 tert.                                                      8 OC.sub.4 H.sub.9 iso                                                                    n.sub.D.sup.25 1.5538                                             9 OCH(CH.sub.3)C.sub.3 H.sub.7 n                                              10                                                                              OCH(CH.sub.3)C.sub.5 H.sub.11 n                                             11                                                                              OC.sub.8 H.sub.17 n                                                         12                                                                              OC.sub.2 H.sub.4 OCH.sub.3                                                              n.sub.D.sup.25 1.5547                                             13                                                                              OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                           14                                                                              OC.sub.2 H.sub.4 Cl                                                                     n.sub.D.sup.25 1.5722                                             15                                                                              OC.sub.2 H.sub. 4 Br                                                          16                                                                             ##STR13##                                                                              n.sub.D.sup.30 1.5617                                               17                                                                             ##STR14##                                                                    18                                                                             ##STR15##                                                                              n.sub.D.sup.30 1.5565                                               19                                                                            OCH.sub.2 CHCH.sub.2                                                                    n.sub.D.sup.25 1.5629                                             20                                                                              OC.sub.2 H.sub.4CHCH.sub.2                                                  21                                                                              OCH.sub.2 C(CH.sub.3)CH.sub.2                                               22                                                                              OCH.sub.2 CCH                                                                           m.p. 64-68°                                                23                                                                              OCH(CH.sub.3)CCH                                                              24                                                                             ##STR16##                                                                    25                                                                             ##STR17##                                                                  26                                                                              OCH.sub.2 CN                                                                  27                                                                            OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                                     n.sub.D.sup.30 1.5445                                             28                                                                              SCH.sub.3 n.sub.D.sup.25 1.5850                                             29                                                                              SC.sub.2 H.sub.5                                                            30                                                                              SC.sub.3 H.sub.7 n                                                          31                                                                              SC.sub.3 H.sub.7 iso                                                        32                                                                              SC.sub.4 H.sub.9 iso                                                        33                                                                              SCH.sub.2 CHCH.sub.2                                                        34                                                                              SCH.sub.2CHCHCH.sub.3                                                       35                                                                              SCH.sub.2 COOCH.sub.3                                                                   n.sub.D.sup.40 1.5788                                               36                                                                             ##STR18##                                                                    37                                                                            O.sup.⊖ Na.sup.⊕                                                            m.p. 98-101                                                       38                                                                              O.sup.⊖ NH.sub.4.sup.⊕                                          39                                                                              NH.sub.2  m.p. 142-5°                                                40                                                                              N(CH.sub.3).sub.2                                                           41                                                                              NHC.sub.2 H.sub.5                                                                       m.p. 112-5°                                                42                                                                              NHC.sub.2 H.sub.4 OH                                                        43                                                                              NH(CH.sub.2).sub.3 OCH.sub.3                                                            m.p. 90-92°                                                44                                                                              NHC.sub.2 H.sub.4 OCH.sub.3                                                             m.p. 89-91°                                                45                                                                              NHC.sub.2 H.sub.4 Cl                                                        46                                                                              NHCH.sub.2 CHCH.sub.2                                                                   m.p. 119-120°                                              47                                                                              N(CH.sub.2 CHCH.sub.2).sub.2                                                48                                                                              NHC.sub.3 H.sub.7 iso                                                       49                                                                              N(C.sub.2 H.sub.5).sub.2                                                                m.p. 73-4°                                                 50                                                                              NHC.sub.4 H.sub.9 n                                                         51                                                                              NHC.sub.5 H.sub.11 iso                                                        52                                                                             ##STR19##                                                                    53                                                                             ##STR20##                                                                              m.p. 39-42°                                                  54                                                                            NHCH.sub.2 COOC.sub.2 H.sub.5                                               55                                                                              N(CH.sub.3)OCH.sub.3                                                                    m.p. 75-7°                                                 56                                                                              ONC(CH.sub.3)C.sub.2 H.sub.5                                                57                                                                              ONC(CH.sub.3).sub.2                                                           58                                                                             ##STR21##                                                                  ______________________________________                                         ##STR22##                                                                      No.       B                   phys. data                                    ______________________________________                                        59                                                                              OCH.sub.3                                                                   60                                                                              OC.sub.2 H.sub.5                                                            61                                                                              OCH.sub.2CHCH.sub.2                                                         62                                                                              OC.sub.3 H.sub.6 OCH.sub.3                                                  63                                                                              SCH.sub.3                                                                   64                                                                              SCH.sub.2 CCH                                                               65                                                                              NHCH.sub.3                                                                  66                                                                              N(CH.sub.3)OCH.sub.3                                                                    n.sub.D.sup.30 1.5613                                             ______________________________________                                         ##STR23##                                                                      No.       B                   phys. data                                    ______________________________________                                        67                                                                              OCH.sub.3 m.p. 88-89°                                                68                                                                              OC.sub.2 H.sub.5                                                                        n.sub.D.sup.30 1.5620                                             69                                                                              OC.sub.3 H.sub.7 iso                                                                    n.sub.D.sup.30 1.5563                                             70                                                                              OC.sub.4 H.sub.9 iso                                                        71                                                                              OC.sub.2 H.sub.4 OCH.sub.3                                                  72                                                                              OCH.sub.2 CN                                                                73                                                                              ONC(CH.sub.3).sub.2                                                         74                                                                              OCH.sub.2 COOCH.sub.3                                                       75                                                                              SCH.sub.3                                                                   76                                                                              SC.sub.3 H.sub.7 iso                                                        77                                                                              SC.sub.5 H.sub.11 n                                                         78                                                                              NH.sub.2                                                                    79                                                                              NHC.sub.2 H.sub.5                                                                       m.p. 104-5°                                                80                                                                              N(C.sub.2 H.sub.5).sub.2                                                    81                                                                              NHCH.sub.3                                                                  82                                                                              NHCH.sub.2 CHCH.sub.2                                                       83                                                                              NHCH.sub.2 CCH                                                              84                                                                              N(CH.sub.3)OCH.sub.3                                                                    n.sub.D.sup.25 1.5660                                               85                                                                             ##STR24##                                                                    86                                                                             ##STR25##                                                                  ______________________________________                                         ##STR26##                                                                      No.       B                   phys. data                                    ______________________________________                                        87                                                                              OCH.sub.3 m.p. 107-8°                                                88                                                                              OC.sub.2 H.sub.5                                                            89                                                                              OC.sub.3 H.sub.7 n                                                          90                                                                              OC.sub.3 H.sub.7 iso                                                                    n.sub.D.sup.30 1.5638                                             91                                                                              OC.sub.4 H.sub.9 n                                                          92                                                                              OC.sub.4 H.sub.9 sec.                                                                   n.sub.D.sup.30 1.5630                                             93                                                                              OCH(CH.sub.3)C.sub.4 H.sub.9 n                                              94                                                                              OC.sub.8 H.sub.17 n                                                         95                                                                              OC.sub.2 H.sub.4 OCH.sub.3                                                              n.sub.D.sup.30 1.5709                                             96                                                                              OCH(CH.sub.3)COOCH.sub.3                                                    97                                                                              OC.sub.2 H.sub.4 Cl                                                         98                                                                              OCH.sub.2 CHCH.sub.2                                                                    n.sub.D.sup.30 1.5771                                             99                                                                              OCH.sub.2 C(CH.sub.3)CH.sub.2                                               100                                                                             OCH.sub.2 CCH                                                                 101                                                                            ##STR27##                                                                    102                                                                           OCH(CH.sub.3)C CH                                                           103                                                                             OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                      n.sub.D.sup.40 1.5699                                               104                                                                            ##STR28##                                                                    105                                                                            ##STR29##                                                                    106                                                                           SCH.sub.3                                                                   107                                                                             SC.sub.2 H.sub.5                                                            108                                                                             SC.sub.4 H.sub.9 iso                                                        109                                                                             SCH.sub.2 CHCH.sub.2                                                        110                                                                             SCH.sub.2 C(CH.sub.3)CH.sub.2                                                           n.sub.D.sup.30 1.5920                                             111                                                                             SCH.sub.2 CCH                                                                           m.p. 92-95°                                                112                                                                             NH.sub.2  m.p. 135-7°                                                113                                                                             NHCH.sub.3                                                                              m.p. 126-7°                                                114                                                                             N(CH.sub.3).sub.2                                                                       m.p. 116-7°                                                115                                                                             NHC.sub.2 H.sub.5                                                                       m.p. 128-9°                                                116                                                                             N(C.sub.2 H.sub. 5).sub.2                                                               m.p. 88-9°                                                 117                                                                             NHC.sub.3 H.sub.7 n                                                                     m.p. 112-4°                                                118                                                                             NHC.sub.3 H.sub.7 iso                                                                   m.p. 112-3°                                                119                                                                             NHCH.sub.2 CHCH.sub.2                                                                   m.p. 108-11°                                               120                                                                             N(CH.sub.2 CHCH.sub.2).sub.2                                                            n.sub.D.sup.30 1.5760                                             121                                                                             NHCH.sub.2 CCH                                                                          m.p. 148-150°                                              122                                                                             NHC.sub.4 H.sub.9 n                                                         123                                                                             NHC.sub.4 H.sub.9 sec.                                                      124                                                                             NHC.sub.4 H.sub.9 iso                                                       125                                                                             NHC.sub.5 H.sub.11 iso                                                                  m.p. 95-98°                                                126                                                                             NHC.sub.6 H.sub.13 n                                                                    m.p. 87-90°                                                127                                                                             NHC.sub.2 H.sub.4 OCH.sub.3                                                             m.p. 101-3°                                                128                                                                             NH(CH.sub.3)OCH.sub.3                                                                   m.p. 93-4°                                                 129                                                                             NHC(CH.sub.3).sub.2 CCH                                                                 m.p. 118-120°                                              130                                                                             NHCH.sub.2 COOC.sub.2 H.sub.5                                                 131                                                                            ##STR30##                                                                              m.p. 116-8°                                                  132                                                                            ##STR31##                                                                              m.p. 118-120°                                                133                                                                            ##STR32##                                                                              m.p. 113-116°                                                134                                                                            ##STR33##                                                                              m.p. 132-134°                                                135                                                                            ##STR34##                                                                              m.p. 130-132°                                                136                                                                            ##STR35##                                                                    137                                                                            ##STR36##                                                                              m.p. 148-151°                                                138                                                                            ##STR37##                                                                              m.p. 134-137°                                                139                                                                            ##STR38##                                                                              m.p. 117-119°                                                140                                                                           NHC.sub.3 H.sub.6 OC.sub.2 H.sub.5                                          141                                                                             NHC.sub.3 H.sub.6 OCH.sub.3                                                             n.sub.D.sup.40 1.5738                                             142                                                                             NHC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                          143                                                                             NHC.sub.8 H.sub.17 n                                                        144                                                                             OH        m.p. 134-6°                                                145                                                                             O.sup.⊖ NH.sub.3 C.sub.3 H.sub.7 iso                                146                                                                             ONC(CH.sub.3).sub.2                                                         ______________________________________                                         ##STR39##                                                                      No.       B                   phys. data                                    ______________________________________                                        147                                                                             OH                                                                          148                                                                             OCH.sub.3 m.p. 80-2°                                                 149                                                                             OC.sub.2 H.sub.5                                                                        n.sub.D.sup.25 1.5511                                             150                                                                             OC.sub.3 H.sub.7 n                                                          151                                                                             OC.sub.3 H.sub.7 iso                                                                    n.sub.D.sup.30 1.5585                                             152                                                                             OC.sub.4 H.sub.9 n                                                          153                                                                             OC.sub.4 H.sub.9 sec.                                                                   n.sub.D.sup.30 1.5590                                             154                                                                             OC.sub.2 H.sub.4 Cl                                                         155                                                                             OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                      n.sub.D.sup.30 1.5715                                               156                                                                            ##STR40##                                                                    157                                                                           OC.sub.2 H.sub.4 OCH.sub.3                                                  158                                                                             OC.sub.3 H.sub.6 OCH.sub.3                                                  159                                                                             OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                         160                                                                             OCH.sub.2 CN                                                                161                                                                             OCH(CH.sub.3)COOC.sub.2 H.sub.5                                                         n.sub.D.sup.30 1.5525                                             162                                                                             ONC(CH.sub.3).sub.2                                                                     n.sub.D.sup.30 1.5665                                             163                                                                             OCH.sub.2 CHCH.sub.2                                                                    n.sub.D.sup.30 1.5735                                             164                                                                             OCH.sub.2 CHCHCH.sub.3                                                      165                                                                             OCH(CH.sub.3)CHCH.sub.2                                                     166                                                                             OCH.sub.2 CCH                                                                           n.sub.D.sup.30 1.5795                                             167                                                                             OC(CH.sub.3).sub.2 CCH                                                        168                                                                            ##STR41##                                                                    169                                                                            ##STR42##                                                                    170                                                                            ##STR43##                                                                              m.p. 145-7°                                                  171                                                                            ##STR44##                                                                    172                                                                           SCH.sub.3 n.sub.D.sup.30 1.6015                                             173                                                                             SC.sub.2 H.sub.5                                                                        n.sub.D.sup.30 1.5933                                             174                                                                             SC.sub.4 H.sub.9 iso                                                        175                                                                             SCH.sub.2 COOCH.sub.3                                                       176                                                                             NH.sub.2  m.p. 156-9°                                                177                                                                             NHCH.sub.3                                                                              m.p. 132-4°                                                178                                                                             N(CH.sub.3).sub.2                                                                       m.p. 118-120°                                              179                                                                             NHC.sub.2 H.sub.5                                                           180                                                                             N(C.sub.2 H.sub.5).sub.2                                                    181                                                                             NHC.sub.3 H.sub.7 iso                                                         182                                                                            ##STR45##                                                                    183                                                                           NHCH.sub.2 COOCH.sub.3                                                        184                                                                            ##STR46##                                                                    185                                                                            ##STR47##                                                                     186                                                                          NHC.sub.2 H.sub.4 OCH.sub.3                                                             m.p. 118-120°                                              187                                                                             NHC.sub.3 H.sub.6 OCH.sub.3                                                             m.p. 90-92°                                                188                                                                             NHCH.sub.2 CHCH.sub.2                                                                   m.p. 104-6°                                                189                                                                             N(CH.sub.2 CHCH.sub.2).sub.2                                                190                                                                             N(CH.sub.3)OCH.sub. 3                                                                   n.sub.D.sup.30 1.5800                                             191                                                                             NHOCH.sub.2 CHCH.sub.2                                                      ______________________________________                                         ##STR48##                                                                      No.       B                   phys. data                                    ______________________________________                                        192                                                                             OCH.sub.3 m.p. 75°                                                   193                                                                             OC.sub.2 H.sub.5                                                            194                                                                             OC.sub.3 H.sub.7 iso                                                                    m.p. 60-3°                                                 195                                                                             OCH(CH.sub.3)C.sub.3 H.sub.7 n                                                          n.sub.D.sup.30 1.5561                                             196                                                                             OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                       n.sub.D.sup.30 1.5631                                             197                                                                             OC.sub.2 H.sub.4 Cl                                                                     n.sub.D.sup.30 1.5792                                             198                                                                             OC.sub.8 H.sub.17 n                                                                     n.sub.D.sup.30 1.5458                                             199                                                                             OCH.sub.2 CHCHCH.sub.3                                                                  n.sub.D.sup.30 1.5730                                             200                                                                             OCH.sub.2 CCH                                                                           m.p. 80-82°                                                  201                                                                            ##STR49##                                                                              n.sub.D.sup.30 1.5811                                               202                                                                           SC.sub.3 H.sub.7 iso                                                                    n.sub.D.sup.30 1.5795                                             203                                                                             SC.sub.4 H.sub.9 iso                                                                    n.sub.D.sup.30 1.5805                                             204                                                                             SCH.sub.2 COOCH.sub.3                                                                   n.sub.D.sup.30 1.5780                                             205                                                                             SCH(CH.sub.3)C.sub.2 H.sub.5                                                            n.sub.D.sup.30 1.5778                                             206                                                                             NH.sub.2  m.p. 155-156°                                              207                                                                             NHC.sub.2 H.sub.5                                                                       m.p. 114-115°                                              208                                                                             N(CH.sub.3)OCH.sub.3                                                        209                                                                             OH        m.p. 150-1°                                                ______________________________________                                         ##STR50##                                                                      No.       B                   phys. data                                    ______________________________________                                        210                                                                             OCH.sub.3 m.p. 74-77°                                                211                                                                             OC.sub.2 H.sub.5                                                            212                                                                             OC.sub.3 H.sub.7 n                                                          213                                                                             OC.sub.3 H.sub.7 iso                                                        214                                                                             OC.sub.4 H.sub.9 iso                                                        215                                                                             OC.sub.6 H.sub.13 n                                                         216                                                                             OC.sub.2 H.sub.4 Cl                                                         217                                                                             OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                          218                                                                             OC.sub. 2 H.sub.4 OC.sub.4 H.sub.9                                            219                                                                            ##STR51##                                                                    220                                                                            ##STR52##                                                                    221                                                                            ##STR53##                                                                    222                                                                           OCH.sub.2 CHCH.sub.2                                                        223                                                                             OCH(CH.sub.3)CHCH.sub.2                                                     224                                                                             OCH.sub.2 CCH                                                               225                                                                             OCH(CH.sub.3)CCH                                                            226                                                                             SCH.sub.3                                                                   227                                                                             SCH.sub.2 CHCH.sub.2                                                        228                                                                             SCH(CH.sub.3)CHCH.sub.2                                                     229                                                                             SCH.sub.2 CCH                                                                 230                                                                            ##STR54##                                                                    231                                                                            ##STR55##                                                                    232                                                                           OH                                                                          233                                                                             O.sup.⊖ H.sub.3 N.sup.⊕ (C.sub.3 H.sub.7 iso).sub.2             234                                                                             O.sup.⊖ Na.sup.⊕                                                235                                                                             O.sup.⊖ NH.sub.4.sup.⊕                                          236                                                                             NH.sub.2                                                                    237                                                                             NHCH.sub.3                                                                  238                                                                             N(C.sub.2 H.sub.5).sub.2                                                    239                                                                             NHC.sub.4 H.sub.9 iso                                                       240                                                                             NHC.sub.2 H.sub.4 OCH.sub.3                                                 241                                                                             NHC.sub.3 H.sub.6 OC.sub.2 H.sub.5                                          242                                                                             N(CH.sub.3)OCH.sub.3                                                        ______________________________________                                         ##STR56##                                                                      No.       B                   phys. data                                    ______________________________________                                        243                                                                             OH                                                                          244                                                                             OCH.sub.3                                                                   245                                                                             OC.sub.3 H.sub.7 iso                                                        246                                                                             OC.sub.4 H.sub.9 n                                                          247                                                                             SCH.sub.3                                                                   248                                                                             SCH.sub.2CHCH.sub.2                                                         249                                                                             SCH.sub.2 COOCH.sub.3                                                       250                                                                             SC.sub.2 H.sub.4 OCH.sub.3                                                  251                                                                             SC.sub.4 H.sub.9 iso                                                          252                                                                            ##STR57##                                                                    253                                                                            ##STR58##                                                                     254                                                                          NH.sub.2                                                                    255                                                                             NHC.sub.2 H.sub.5                                                           256                                                                             N(CH.sub.3).sub.2                                                           257                                                                             NHCH.sub.2 CHCH.sub.2                                                       258                                                                             N(CH.sub.3)OCH.sub.3                                                        259                                                                             NHC.sub.5 H.sub.11 n                                                        ______________________________________                                         ##STR59##                                                                      No.       B                   phys. data                                    ______________________________________                                        260                                                                             OH                                                                          261                                                                             OCH.sub.3 n.sub.D.sup.25 1.5150                                             262                                                                             OC.sub.2 H.sub.5                                                            263                                                                             OC.sub.3 H.sub.7 n                                                          264                                                                             OC.sub.3 H.sub.7 iso                                                        265                                                                             OCH.sub.2 CHCH.sub.2                                                        266                                                                             OCH.sub.2 CCH                                                               267                                                                             OCH(CH.sub.3)COOC.sub.2 H.sub.5                                             268                                                                             NH.sub.2                                                                    269                                                                             NHCH.sub.3                                                                  270                                                                             N(CH.sub.3).sub.2                                                           271                                                                             N(C.sub.3 H.sub.7 iso).sub.2                                                272                                                                             NHCH.sub.2 CHCH.sub.2                                                       273                                                                             NHCH.sub.2 CHCH                                                             ______________________________________                                         ##STR60##                                                                      No.       B                   phys. data                                    ______________________________________                                        274                                                                             OH                                                                          275                                                                             OCH.sub.3 m.p. 74-75°                                                276                                                                             OC.sub.2 H.sub.5                                                            277                                                                             OCH.sub.2 CN                                                                278                                                                             OC.sub.3 H.sub.7 n                                                          279                                                                             OC.sub.3 H.sub.7 iso                                                        280                                                                             OC.sub.4 H.sub.9 n                                                          281                                                                             OCH.sub.2 CHCH.sub.2                                                        282                                                                             OCH.sub.2 CHCHCH.sub.3                                                      283                                                                             OCH.sub.2 CCH                                                               284                                                                             SCH.sub.3                                                                   285                                                                             SC.sub.2 H.sub.5                                                            286                                                                             SC.sub.3 H.sub.7 iso                                                        287                                                                             SCH.sub.2 CN                                                                288                                                                             SCH.sub.2 COOCH.sub.3                                                       289                                                                             NH.sub.2                                                                    290                                                                             NHCH.sub.3                                                                  291                                                                             N(CH.sub.3).sub.2                                                           292                                                                             NH(C.sub.3 H.sub.7 iso)                                                     293                                                                             NHCH.sub.2 CHCH.sub.2                                                         294                                                                            ##STR61##                                                                  ______________________________________                                         ##STR62##                                                                      No.       B                   phys. data                                    ______________________________________                                        295                                                                             OH                                                                          296                                                                             OCH.sub.3                                                                   297                                                                             OC.sub.2 H.sub.5                                                                        n.sub.D.sup.30 1.5223                                             298                                                                             OC.sub.3 H.sub.7 n                                                          299                                                                             OC.sub.4 H.sub.9 iso                                                        300                                                                             OCH.sub.2 CHCH.sub.2                                                        301                                                                             OCH.sub.2 CCH                                                               302                                                                             OCH(CH.sub.3)CCH                                                            303                                                                             OC.sub.4 H.sub.9 n                                                          304                                                                             OC.sub.4 H.sub.9 tert.                                                      305                                                                             OC.sub.4 H.sub.9 sec.                                                       306                                                                             OC.sub.2 H.sub.4 OCH.sub.3                                                  307                                                                             OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                         308                                                                             OC.sub.2 H.sub.4 Cl                                                         309                                                                             OC.sub.2 H.sub.4 Br                                                         310                                                                             OCH.sub.2 CHCHCH.sub.2 Cl                                                   311                                                                             OCH.sub.2 C(CH.sub.3)CH.sub.2                                               312                                                                             OC.sub.2 H.sub.4 N(CH.sub.3).sub. 2                                         313                                                                             OC.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                   314                                                                             OCH(CH.sub.3)COOC.sub.2 H.sub.5                                             315                                                                             OCH(C.sub.2 H.sub.5).sub.2                                                  316                                                                             SH                                                                          317                                                                             SCH.sub.3                                                                   318                                                                             SC.sub.2 H.sub.5                                                            319                                                                             SCH.sub.2 COOC.sub.2 H.sub.5                                                320                                                                             SCH.sub.2 CHCH.sub.2                                                        321                                                                             SCH.sub.2 CCH                                                               322                                                                             SC.sub.4 H.sub.9 n                                                          323                                                                             SCH.sub.2CH(CH.sub.3)CH.sub.2                                               324                                                                             SCH(CH.sub.3)CCH                                                            325                                                                             NH.sub.2  m.p. 127-128°                                              326                                                                             NHC.sub.2 H.sub.4 OCH.sub.3                                                 327                                                                             NHC.sub.3 H.sub.6 OCH.sub.3                                                 328                                                                             N(C.sub.2 H.sub.4 OH).sub.2                                                 329                                                                             NHC.sub.2 H.sub.4 COOCH.sub.3                                               330                                                                             NHCH.sub.2 COOCH.sub.3                                                      331                                                                             NHC.sub.2 H.sub.4 OH                                                        332                                                                             NHCH.sub.3                                                                              m.p. 113-114°                                              333                                                                             N(CH.sub.3).sub.2                                                           334                                                                             NHC.sub.2 H.sub.5                                                           335                                                                             N(C.sub.2 H.sub.5).sub.2                                                    336                                                                             NHC.sub.3 H.sub.7 n                                                         337                                                                             NHC.sub.4 H.sub.9 n                                                           338                                                                            ##STR63##                                                                    339                                                                           N(CH.sub.3 )OCH.sub.3                                                       ______________________________________                                         ##STR64##                                                                      No.       B                   phys. data                                    ______________________________________                                        340                                                                             OH                                                                          341                                                                             OCH.sub.3 m.p. 89-93°                                                342                                                                             OC.sub.2 H.sub.5                                                                        n.sub.D.sup.20 1.5340                                             343                                                                             OCH.sub.2 CHCH.sub.2                                                        344                                                                             SCH.sub.2 CHCH.sub.2                                                        345                                                                             SCH.sub.3                                                                   346                                                                             SCH.sub.2 COOCH.sub.3                                                       347                                                                             NH.sub.2                                                                    348                                                                             NHCH.sub.3                                                                  349                                                                             N(CH.sub.3).sub.2                                                           350                                                                             NHC.sub.2 H.sub.5                                                           351                                                                             NHCH.sub.2 CHCH.sub.2                                                       ______________________________________                                         ##STR65##                                                                      No.       B                   phys. data                                    ______________________________________                                         352                                                                            OH                                                                          353                                                                             OCH.sub.3                                                                   354                                                                             OC.sub.2 H.sub.5                                                                        n.sub.D.sup.30 1.5167                                             355                                                                             OC.sub.3 H.sub.7 iso                                                        356                                                                             OC.sub.2 H.sub.4 OCH.sub.3                                                  357                                                                             OCH.sub.2 CHCH.sub.2                                                        358                                                                             OCH.sub.2CH                                                                 359                                                                             SCH.sub.3                                                                   360                                                                             SC.sub.2 H.sub.5                                                            361                                                                             SCH.sub.2 CHCH.sub.2                                                        362                                                                             NH.sub.2                                                                    363                                                                             N(CH.sub.3).sub.2                                                           364                                                                             NHC.sub.2 H.sub.5                                                           365                                                                             NHC.sub.2 H.sub.4 OCH.sub.3                                                 366                                                                             N(CH.sub.3)OCH.sub.3                                                        ______________________________________                                         ##STR66##                                                                      No.     E      D    Z    B          phys. data                              ______________________________________                                        367                                                                             Cl      Br     Cl   OCH.sub.3                                               368                                                                             Cl      Br     Cl   OC.sub.2 H.sub.5                                        369                                                                             I       H      NO.sub.2                                                                           OCH.sub.3                                                                          n.sub.D.sup.25 1.6125                              370                                                                             I       H      Cl   OCH.sub.3                                                                          n.sub.D.sup.25 1.5995                              371                                                                             Br      Br     NO.sub.2                                                                           OCH.sub.3                                                                          m.p. 118-120°                               372                                                                             CN      Cl     Cl   OCH.sub.3                                                                          m.p. 109-111°                               373                                                                             Br      CN     Cl   OCH.sub.3                                                                          m.p. 135-7°                                 374                                                                             Cl      H      Cl   OCH.sub.3                                                                          b.p. 145-150°/0.04                          375                                                                             Cl      H      NO.sub.2                                                                           NH.sub.2                                                376                                                                             Br      H      NO.sub.2                                                                           OC.sub.2 H.sub.5                                        377                                                                             Br      H      Cl   OCH.sub.2 CHCH.sub.2                                    378                                                                             CN      Cl     Br   OCH.sub.3                                                                          m.p. 107-9°                                 379                                                                             CF.sub.3                                                                              Cl     Br   OCH.sub.3                                               380                                                                             Cl      CH.sub.3                                                                             Cl   OCH.sub.3                                               381                                                                             Cl      CH.sub.3                                                                             Br   OC.sub.2 H.sub.5                                        382                                                                             Cl      CH.sub.3                                                                             NO.sub.2                                                                           OCH.sub.3                                               383                                                                             Cl      CH.sub.3                                                                             NO.sub.2                                                                           NHCH.sub.3                                              384                                                                             CF.sub.3                                                                              H      Br   OCH.sub.3                                               385                                                                             CF.sub.3                                                                              Br     Cl   OCH.sub.3                                               386                                                                             Br      Br     Br   OCH.sub.3                                                                          m.p. 64-6°                                  387                                                                             Br      Br     NO.sub.2                                                                           OCH.sub.3                                                                          m.p. 118-120°                               388                                                                             Br      Br     Br   SCH.sub.3                                               389                                                                             Br      Br     Cl   OCH.sub.3                                                                          m.p. 86-8°                                  390                                                                             Cl      H      Br   OCH.sub.3                                                                          m.p. 80-2°                                  391                                                                             CF.sub.3                                                                              Br     NO.sub.2                                                                           NH.sub.2                                                392                                                                             CF.sub.3                                                                              Br     NO.sub.2                                                                           NHCH.sub.3                                              ______________________________________                                         ##STR67##                                                                      No.     E      D    Z    B          phys. data                              ______________________________________                                        393                                                                             Cl      Br     NO.sub.2                                                                           OC.sub.2 H.sub.5                                                                   n.sub.D.sup.25 1.5820                              394                                                                             CN      Cl     NO.sub.2                                                                           OC.sub.2 H.sub.5                                        395                                                                             Cl      CH.sub.3                                                                             NO.sub.2                                                                           OC.sub.2 H.sub.5                                        396                                                                             Cl      CH.sub.3                                                                             NO.sub.2                                                                           NH.sub.2                                                397                                                                             Br      Br     NO.sub.2                                                                           OC.sub.2 H.sub.5                                        398                                                                             CF.sub.3                                                                              Br     NO.sub.2                                                                           OC.sub.2 H.sub.5                                        ______________________________________                                         ##STR68##                                                                      No.     E      D    Z    B          phys. data                              ______________________________________                                        399                                                                             Cl      Cl     NO.sub.2                                                                           OCH.sub.3                                                                          m.p. 83-5°                                  400                                                                             Cl      Cl     NO.sub.2                                                                           NH.sub.2                                                                           m.p. 203-5°                                 401                                                                             Cl      Cl     NO.sub.2                                                                           NHC.sub.2 H.sub.5                                                                  m.p. 124-5°                                 402                                                                             Cl      Cl     NO.sub.2                                                                           N(CH.sub.3)OCH.sub.3                                                               m.p. 106-7°                                 403                                                                             Cl      Cl     NO.sub.2                                                                           OC.sub.2 H.sub.4 OCH.sub.3                                                         m.p. 71-2°                                  404                                                                             Cl      Cl     Br   OCH.sub.3                                                                          m.p. 81-2°                                  405                                                                             Cl      CH.sub.3                                                                             NO.sub.2                                                                           OCH.sub.3                                               406                                                                             CF.sub.3                                                                              Cl     NO.sub.2                                                                           OCH.sub.3                                               407                                                                             CF.sub.3                                                                              H      NO.sub.2                                                                           OCH.sub.2 CHCH.sub.2                                    408                                                                             CF.sub.3                                                                              H      Cl   OCH.sub.3                                               409                                                                             CF.sub.3                                                                              Cl     Cl   OCH.sub.3                                               ______________________________________                                         ##STR69##                                                                      No.     E      D    Z    B          phys. data                              ______________________________________                                        410                                                                             Cl      Cl     Cl   OCH.sub.3                                                                          n.sub.D.sup.30 1.5586                              411                                                                             Cl      Cl     NO.sub.2                                                                           OCH.sub.3                                                                          n.sub.D.sup.30 1.5527                              412                                                                             Cl      Cl     NO.sub.2                                                                           OC.sub.2 H.sub.5                                        413                                                                             Cl      Cl     NO.sub.2                                                                           NHCH.sub.3                                              414                                                                             CF.sub.3                                                                              H      NO.sub.2                                                                           OCH.sub.3                                               415                                                                             CF.sub.3                                                                              Cl     NO.sub.2                                                                           OC.sub.2 H.sub.5                                        416                                                                             CF.sub.3                                                                              Cl     Cl   OCH.sub.3                                               417                                                                             Br      Br     NO.sub.2                                                                           OCH.sub.3                                               ______________________________________                                         ##STR70##                                                                      No.       B                   phys. data                                    ______________________________________                                        418                                                                             OCH.sub.3 m.p. 93-94°                                                419                                                                             OC.sub.2 H.sub.5                                                            420                                                                             OC.sub.2 H.sub.4 OCH.sub.3                                                  421                                                                             NH.sub.2  m.p. 145-146°                                              422                                                                             NHCH.sub.3                                                                              m.p. 132-134°                                              423                                                                             N(CH.sub.3).sub.2                                                                       m.p. 136-137°                                              424                                                                             NHC.sub.2 H.sub.5                                                                       m.p. 124-126°                                              425                                                                             N(C.sub.2 H.sub.5).sub.2                                                                m.p. 75-77°                                                ______________________________________                                         ##STR71##                                                                      No.      E     D   Z    R.sub.1                                                                            A          phys. data                          ______________________________________                                        426                                                                             Cl       Cl    NO.sub.2                                                                          H    CN   m.p. 118-120°                           427                                                                             Cl       Cl    Cl  CH.sub.3                                                                           CN   m.p. 119-120°                           428                                                                             Cl       Cl    Cl  H    CN   m.p. 101-3°                               429                                                                           Cl       Cl    Cl  CH.sub.3                                                                            ##STR72##                                                                         m.p. 133-5°                               430                                                                           Cl       Cl    Cl  CH.sub.3                                                                            ##STR73##                                            431                                                                           Cl       Cl    NO.sub.2                                                                          CH.sub.3                                                                            ##STR74##                                          ______________________________________                                    

The compositions of the present invention are obtained in known mannerby homogeneously mixing and grinding active substances of the generalformula I with suitable carriers, with or without the addition ofdispersants or solvents which are inert to the active substances. Theactive substances can be processed to the following formulations:

solid formulations:

dusts, tracking powders, granules (coated granules, impregnated granulesand homogeneous granules);

active substance concentrates which are dispersible in water:

wettable powders, pastes, emulsions;

liquid formulations: solutions.

The concentration of active substance in the above describedcompositions is between 0.1 and 95%, preferably between 1 and 80%. Therates of application are ordinarily from 0.1 to 10 kg, preferably from0.25 to 5 kg, of active substance per hectare. The compositions of thepresent invention can also be mixed with other biocidal activesubstances or compositions.

The active substances of the formula I can be formulated for example asfollows (parts are by weight):

Dusts

The following substances are used to prepare

(a) 5% and (b) a 2% dust:

(a)

5 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenoxy]propionicacid methyl ester,

95 parts of talc;

(b)

2 parts of active substance

1 part of highly dispersed silicic acid

97 parts of talc.

The active substances are mixed with the carriers and ground.

Granulate

The following substances are used to prepare a 5% granulate:

5 parts of the above active substance

0.25 parts of epichlorohydrin

0.25 parts of cetyl polyglycol ether

3.25 parts of polyethylene glycol

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture isdissolved in 6 parts of acetone. Then polyethylene glycol and cetylpolyglycol ether are added. The resulting solution is sprayed on kaolinand subsequently evaporated in vacuo.

Wettable Powders

The following constituents are used to prepare (a) a 50%, (b) a 25% and(c) a 10% wettable powder:

(a)

50 part of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenoxy]propionicacid methyl ester

5 parts of sodium dibutylnaphthylsulphonate

3 parts of naphthalenesulphonic acid/phenolsulphonic acid/formaldehydecondensate (3:2:1)

20 parts of kaolin

22 parts of Champagne chalk;

(b)

25 parts of the above active substance

5 parts of sodium oleylmethyltauride

2.5 parts of naphthalenesulphonic acid/formaldehyde condensate

0.5 parts of carboxymethyl cellulose

5 parts of neutral potassium aluminium silicate

62 parts of kaolin;

(c)

10 parts of the above active substance

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates

5 parts of naphthalenesulphonic acid/formaldehyde condensate

82 parts of kaolin.

The indicated active substance is applied to the corresponding carriers(kaolin and chalk) and then these are mixed and ground, to yieldwettable powders of excellent wettability and suspension power. Bydiluting these wettable powders with water it is possible to obtainsuspensions of the desired concentration of active substance. Suchsuspensions are used for controlling weeds and grass-like weeds in cropsof cultivated plants by the preemergent method and for treating areas ofgrass.

Paste

The following substances are used to manufacture a 45% paste:

45 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-nitrophenoxy]propionicacid methyl ester

5 parts of sodium aluminium silicate

14 parts of cetyl polyglycol ether with 8 moles of the ethylene oxide

1 part of oleyl polyglycol ether with 5 moles of the ethylene oxide

2 parts of spindle oil

10 parts of polyethylene glycol

23 parts of water.

The active substance is homogeneously mixed with the adjuvants inappropriate devices and ground, yielding a paste from which, by dilutionwith water, it is possible to obtain suspensions of the desiredconcentration of active substance. The suspensions are suitable fortreating areas of grass.

Emulsifiable Concentrate

The following ingredients are mixed to manufacture a 25% emulsifiableconcentrate:

25 parts ofα-[3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenoxy]propionic acidisopropyl ester

5 parts of a mixture of nonylphenolpolyoxyethoxy-ethylene and calciumdodecylenesulphonate

35 parts of 3,3,5-trimethyl-2-cyclohexan-1-one

35 parts of dimethyl formamide.

This concentrate can be diluted with water to give emulsions in thedesired concentrations.

Instead of using the respective active substance indicated in theforegoing formulation examples, it is also possible to use another ofthe compounds comprised by the formula I.

The active substances of the invention are also of interest forcombination with an number of hercides of the phenylurea and triazineseries for use in cereal crops, maize, sugar cane, and in fruit cultureand viticulture.

The active substances of the formula I are distinguished by a verypronounced preemergent herbicidal action and are thus also stronggermination inhibitors.

The following test methods were employed to established the usefulnessof the compounds of the formula I as herbicides (pre- and postemergent).

Preemergent herbicidal action (germination inhibition)

In a greenhouse, immediately after sowing the test plants in seed dishesthe surface of the soil is treated tiwh an aqueous suspension of theactive substances obtained from a 25% wettable powder. A concentrationwas used, which corresponded to 4 kg of active substance per hectare.The seed dishes are then kept in the greenhouse at 22°-25° C. and 50 to70% relative humidity. The test was evaluated 3 weeks later according tothe following rating:

1=plants have not germinated or are totally withered

2-8=intermediate stages of damage

9=plants undamaged (as untreated control).

The results are resumed in the table below:

    ______________________________________                                        Compound          Sinapis    Setaria                                                                             Stellaria                                  number     oats   alba       italica                                                                             media                                      ______________________________________                                         2         8      3          2     2                                           14        9      2          2     3                                           35        9      4          1     2                                           53        7      3          2     2                                           87        2      1          1     3                                          112        2      1          1     1                                          114        1      2          1     2                                          115        1      1          1     1                                          127        2      2          1     2                                          144        9      1          1     5                                          149        7      2          2     2                                          192        9      2          1     1                                          201        9      4          1     1                                          210        2      1          1     1                                          261        2      2          1     7                                          297        1      1          1     1                                          399        3      1          3     9                                          418        9      1          1     1                                          ______________________________________                                    

Post-emergent herbicidal action (Contact herbicide)

A number of weeds and cultivated plants, both mono- and dioctyledonous,were sprayed after emergence in the 4- to 6-leaf stage with an aqueousactive substance emulsion in a rate of 4 kg of active substance perhectare and kept at 24°-26° C. and 45-60% relative humidity. The testwas evaluated, as in the preemergent test, 15 days after treatment inaccordance with the same rating.

The results are resumed in the table below:

    ______________________________________                                        Compound        Setaria   Lolium                                                                              Sinapis Stellaria                             No.      oats   italica   perenne                                                                             alba    media                                 ______________________________________                                         1       2      1         1     1       1                                      2       4      1         2     1       1                                      3       4      1         3     2       2                                      12      7      1         3     1       2                                      16      6      2         3     1       2                                      19      5      1         3     1       2                                      22      6      2         6     2       1                                      27      4      1         2     1       1                                      28      6      1         5     3       2                                      35      5      1         3     1       1                                      41      4      5         4     2       2                                      43      4      1         4     1       1                                      53      5      2         6     1       2                                      55      6      1         3     1       1                                      66      4      1         4     2       3                                      92      2      1         1     1       3                                      95      4      2         3     1       6                                      98      4      1         1     1       2                                     111      4      2         2     1       2                                     113      2      2         2     2       3                                     115      2      2         5     1       5                                     128      2      1         3     1       1                                     129      7      1         6     1       6                                     141      4      3         4     1       4                                     149      2      1         2     1       1                                     192      3      1         1     1       1                                     194      3      1         1     1       1                                     196      3      1         1     1       1                                     200      4      1         2     1       1                                     201      7      1         3     1       1                                     202      6      2         4     2       2                                     204      5      2         3     2       2                                     210      1      1         1     1       1                                     261      1      1         1     1       1                                     297      1      1         1     1       1                                     372      4      2         4     2       1                                     387      2      1         1     1       1                                     399      1      1         2     1       3                                     403      2      1         2     1       8                                     418      4      1         2     1       4                                     426      2      1         3     1       4                                     ______________________________________                                    

We claim:
 1. A compound of the formula ##STR75## wherein Z is chlorineor nitro, R₁ is methyl or ethyl, and B is --O--N═C(C₁ -C₄ alkyl)₂,cyclohexanonoxime or 2,6-dichlorobenzaldehyde-oxime.
 2. A compoundaccording to claim 1 in which Z is nitro and R₁ is methyl.
 3. Thecompound according to claim 2 which isα-[3-3,5-dichloropyridyl-2-oxy)-6-nitrophenoxy]-propionic acidacetonoxime.
 4. The compound according to claim 2 which isα-[3-(3,5-dichloropyridyl-2-oxy)-6-nitrophenoxy]-propionic acid2,6-dichlorobenzaldehyde-oxime.
 5. A herbicidal composition whichcontains as active ingredient a herbicidally effective amount of acompound according to claim 1 together with an inert carrier.
 6. Amethod for controlling weeds at a locus, which comprises applying tosaid locus a herbicidally effective amount of a compound according toclaim
 1. 7. A method according to claim 6 in which, in the compound, Zis nitro and R₁ is methyl.